SU833936A1 - Method of producing aliphatic c-3-c8 hydrocarbons - Google Patents

Description

one

The invention relates to methods for producing aliphatic hydrocarbons and can be used to obtain intermediate products of chemical and petrochemical syntheses.

Known: a method of producing lower aliphatic hydrocarbons from a mixture of gases containing hydrogen, carbon monoxide and carbon dioxide in the presence of iron-based catalysts

Due to the different dosages of KSShi oxide, it is possible to regulate the relative yield of lower, mainly gaseous, aliphatic and higher hydrocarbons. The conversion of carbon monoxide and carbon dioxide is 8498%.

The closest to the proposed method is the production of aliphatic hydrocarbons, by reacting saturated and unsaturated hydrocarbons in the presence of a complex catalyst, with a mixture of alkanes being used as saturated hydrocarbons, and alkenes as unsaturated. The catalyst is a tri-halo galogensulfonog va or methylsulfonic acid, or a mixture thereof with the additive (10-30 vol.% Of the acid) of water, aliphatic alcohols odnoosnovnES nasltsennyh gsulfonovoy acid C -C aromatic series, aliphatic monoesters nasy1 ennyh, diftorfosfornoy acid and a small amount of sulfuric acid 2.

Alkylation proceeds at -29, + 4s and a pressure of 1-20 atm. As a result, a complex mixture of gaseous and liquid hydrocarbon products is formed. :

The disadvantages of the method are the low degree of paraffin conversion of hydrocarbons, the complexity of the composition of the catalyst used, the need to apply pressure, indicating a lack of high catalyst activity, the limited scope of the method

0 (the mixture of alkanes does not include methane) and the difficulty of separating the resulting mixture of hydrocarbons.

The goal of the invention is to increase the degree of conversion of paraffin hydrocarbons and simplify the process.

This aim is achieved produce aliphatic hydrocarbons by reaction of saturated hydrocarbons, as ko0 toryh use paraffin hydrocarbons with unsaturated: acetylene or a mixture of acetylene and ethylene in the presence of hydrogen and of a complex katalizatorag nickel stearate, naphthenate or naftengidroksamata nickel or naftengidroksamata nickel to nickel hydroxide with triethylaluminium. or diisobutylaluminium hydride at a molar spacing of A1 / NI equal to b-10 / at a temperature of 20-40 C and a volume ratio of the reactants acetylene: paraffin hydrocarbons: hydrogen 1: 0.2-10.0: 1-7. The proposed method allows to increase the conversion rate to. The complex catalyst used is uncomplicated in composition and highly active, which allows the process to be carried out at atmospheric pressure. The scope of the process extends to methane, which makes it possible to use cheap for the synthesis of aliphatic hydrocarbons. natural raw materials. The method is carried out as follows. A toluene and a sample of stearate, naphthenate, or nickel naphthenhydroxamate nickel MG (NG), or Y (NG) 2. on Y ((OH) 2 and triethylaluminium or diisobutyl-aluminaIhydride (DEBH) with an AI / Ni ratio of 6-10. it is a gas mixture containing individual paraffinic hydrocarbons, or in smeggs with ethylene, acetylene and hydrogen at a fixed ratio. Periodically, the composition of the gas mixture before and after the reactor is analyzed using a chromatograph.In the absence of paraffinic hydrocarbons, only the selective hydrogenation of acetylene to 1-ethylene, propylene and hydrocarbon proceeds, qj-Gg flows through hydrogenation on an N (Hr) catalyst i - DIBAG, (A1) M 7 and NifHr) 0.57 mmol. in toluene (gas mixtures, o6.% tC.2.H 2. H 2. - 3 and 02.) were not detected. In the absence of hydrogen in a mixture of gases containing CHd,,,, or in the absence of acetylene in a mixture of gases containing H, ..., CjH, the transformation of alkanes does not take place. Example. The mixture of gases soy-, tava,, j, 6,, (the ratio of paraffin hydrocarbons (PU): hydrogen 1: 0.8: 1) the rest of the argon is passed at a speed of 40 ml / min through a catalyst placed in a duck, in 20 ml toluene and consisting of 0.345 g (0.57 mol) M (NG) 2 on a carrier N i (OH) 2 (50 mol.% DIBAG 3.42 kmol, held in a stream of argon for 20 minutes and in a stream of hydrogen for 30 minutes. Outgoing gas contains,%: methane 0.74, ethane 0.02, acetylene 0.72, ethylene 1.69, propylene 0.01, hydrocarbons 3.52, i.e., the methane conversion is 85%. Example 2. In the weft, a catalyst is prepared from 1.14 mmol Ni (Hr) 2 without carrier and 7.98 mia DI AH at 40 ° C in 20 ml of toluene.After 50 minutes of catalyst formation in a stream of hydrogen, technical ethylene is passed through it containing methane, ethane, acetylene (acetylene: PU ratio 1: 3) as an admixture at a rate of 50 ml / min. Through the mixer hydrogen is supplied to the reactor at the rate of: PU: H2 1: 3: 3. Table 1 shows the composition of the gases before and after the reactor and the degree of conversion of paraffin hydrocarbons. Table 1 Example 3. In analogy to Example 2, a catalyst was prepared in a duck with 1.14 mmol of N (NG) 2 on Ni {OH) 2. 7.98 mmol DIBAG in 20 ml of toluene. Through the catalyst technical ethylene is passed at a rate of

25 ml / min and hydrogen at the rate of: H 2.1: 3. The ratio of acetylene: PU from 1: 0.4 (1 and 6-7 hours) to 1: 10.2 (175 hours).

The results are shown in Table. 2

Table

Example 4. Gas mixture coagent,% i C2Nb 1.5; C, H2 1.0; H 3} the rest — ethylene — is passed at a rate of 50 ml / min at 20 ° C through s, flowing a tubular vertical reactor with a nozzle in which there is a kata.

Example 5 Gas mixture soy in example

Tava,%: CH4 0,26 Cyllf, 3,5, CaKJ, 200 ml / min.

H22.25 (1: 5: 3), skip-B table. 4 shows the composition of the gas

the cabin through the catalyst, the amount after the reactor and the degree of conversion

and the composition of which are indicated 65C.Nd and.

lizator. prepared from 0.345 g Ni (Hr) 2 / Wi (OH) 2. 0.57 mmol I1 (NG), 4.0 mmol DIBAG and 20 ml of toluene.

In tab. 3 shows the results of the analysis of the gas after the reactor.

Table3

With an increase in the rate of transmission of a mixture of gases of similar composition (CHL 0.075;;. О, 8, n 2.4;

nViCjHj: At 7 2: 1: 3) to 1000 ml / min

PRI me R 6. gas mixture ssg / tava,%: SP 0.33; R, 95): 1.4; Hji 4 (ratio C2.H: PU: H2 1: 0.9: 2.8), the rest is ethylene, passed through a catalyst prepared on the basis of nickel naphthenate Example 7. Through catalysis-40 torus Ni (HDj / Ni (OH ) a (1 | 71 mmol M1 (NG) 2.),) (mmol) at 40 ° C in toluene technical ethylene is passed with the content,% by volume: CH4 0.36, C-iHfi 0.14, and

conversion rate remains high.

The data presented in Table. five.

Table 5

(1.14 mmol) with DIBAG (6.84 mmol) at a flow rate of 75 ml / min.

The content of methane and ethane in the waste gas after the reactor is given in Table. 6

Table b. The GS2H2 ratio: PU 1GO, 43) at a rate of 25 ml / min. The amount of H fed to the reactor corresponds to the ratio Ij5. The results of gas analysis after the reactor are given in Table. 7. Example 8. The catalyst with a composition of 1.14 mms of nickel stearate 7.98 km DIBAG is prepared in toluopa. when in a metal tubular reactor filled with a glass nozzle. Technical ethylene composition,% by volume: СН4 0.087; 0,, 125; . 1.04 PRI me R 9. Gas composition,%: СН 0.4V, 1.2; , 4 (.tH up to 1: 0.3: 2}, the rest is ethylene, skipping the cabin at 20 ° C through the catalyst Nt. (Hr) i / Ni (OH) - DIBAG A1 / N5

Example 10. Summary of the effect of the amount of hydrogen in the gas mixture () and the nature of the alkyl 60 catalyst catalyst component (ADCjHj-k or DIBAG on the degree of methane conversion in the presence of catalyst Ni (Hr) 4 / Ni (OH) j, at 40 ° C And the gas transmission rate of 25 MP / min b5

Table 7

Table 8

The initial composition of the gas mixture without hydrogen,%: SND 0.4; , 2; SuN 98.4. The amount of catalyst in the experiments on 0.57 mmol Ni (Hr) .L, the ratio of A1 / NI 7.

Summary data are presented in table. 10. and hydrogen (ratio 1. S 0.2: 3) are passed through a catalyst. The flow rate is 25 ml / min. The content of CND and the output and their degree of conversion are presented in Table. 8. 7, aged 50 min in hydrogen ®, the content of methane, propylene and butane, in the gas after the reactor is presented in Table. -9. T a b l And c a 9

Claims (1)

Claim A method of producing aliphatic hydrocarbons CyCg by the interaction of saturated and unsaturated hydrocarbons in the presence of a complex catalyst, characterized in that, in order to increase the degree of conversion of n arguments and simplify the quality of saturated hydrocarbons, C 1 -C 4 paraffin hydrocarbons are used which react with acetylene or a mixture of acetylene 35 and ethylene in the presence of hydrogen and a complex catalyst: nickel stearate, naphthenate or naphthenic -> nickel roxamate or nickel naphthenhydroxamate on idrookisi nickel with triethylaluminium or diisobutylaluminium hydride in a molar ratio Άΐ / Ni, equal to 6-10, D * At temperatures ^of 20-40 C, and a volume ratio of acetylene reagents: paraffin hydrocarbons: hydrogen 1: 0.2-10.0: 1-7 .